US3095417A - Process for the preparation of piperazine - Google Patents

Process for the preparation of piperazine Download PDF

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Publication number
US3095417A
US3095417A US44005A US4400560A US3095417A US 3095417 A US3095417 A US 3095417A US 44005 A US44005 A US 44005A US 4400560 A US4400560 A US 4400560A US 3095417 A US3095417 A US 3095417A
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Prior art keywords
piperazine
monoethanolamine
reaction
hydrohalide
pyrolysis
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US44005A
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Poppelsdorf Fedor
Richard C Myerly
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Union Carbide Corp
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Union Carbide Corp
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Priority to US44005A priority Critical patent/US3095417A/en
Priority to GB25911/61A priority patent/GB979140A/en
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Publication of US3095417A publication Critical patent/US3095417A/en
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D295/00Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/02Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements
    • C07D295/023Preparation; Separation; Stabilisation; Use of additives

Definitions

  • the process of this invention has at least two advantages over the prior arte-it makes possible the economical operation of a process below 250 C. and it provides increased productivities at a given reaction temperature.
  • the tact that the reaction proceeds at temperatures lower than '25 0 C. is important for at least two reasons.
  • The, pyrolysis. of monoethanolamine hydrohalide is a very corrosive reaction.
  • the materials which are used as liners are tantalum, ceramic and glass. It is economically desirable to use glass as a liner'because ofits cost.
  • glass-lined equipment does not stand up satisfactorily at temperatures above 250 C. The process of this invention allows glass to be used since it is conducted below 250 C.
  • the monoethanolamine hydrohalides which can be employed as starting materials are rnonoethanolamine hydrochloride, hydrobromide, hydroiodide and hydrofluoride.
  • the efiect of the catalyst on the yields of piperazine can be shown from the following table in which the catalyst is hydrogen chloride and the hydrohalide is monoethanolamine hydrochloride.
  • the temperatures at which the reaction can be conducted are from about 215 C. to about 250 C.
  • the preferred range is firom 220 C. to 230 C., at atmospheric pressure.
  • Monoethanolarnine hydrohalide is first prepared by treating monoethanolamine with an anhydrous hydrogen halide.
  • the particular proportions are not narrowly critical.
  • the preferred concentration is a 1:1 molar ratio.
  • the monoethanolamine hydrohalide formed is brought to the desired reaction temperature and anhydrous hydrogen halide, preferably hydrogen chloride, is passed through the molten mass with stirring.
  • the amount of catalyst passed through-at atmospheric pressure can be from 0.1
  • the pyrolysis can also be conducted in the presence of an inert dispersant.
  • the nature of the dispersant is not critical. The only condition being that it is inert under the reaction conditions.
  • examples of dispersants include mineral oil, diphenyl ether, phenyl diphenyl ether, etc.
  • the concentration of the dispersant is not critical and 3 can be from 30-l20 grams per mole of amine hydrohalide starting material.
  • reaction mass was held with stirring under these conditions for /2 hours.
  • the product was cooled to about 120 C. and then made strongly alkaline to phenolphthalein by the addition of sodium hydroxide solution (aqueous 50 percent).
  • Diethylenetriamine 500 g. was added to serve as a distillation aid and potboiler after which the mixture was distilled with stirring at atmospheric pressure.
  • Piperazine 94.8 g. was distilled over in a yield of 36.7 percent.
  • the reaction mass was held with stirring under these conditions for 5 hours.
  • the product was cooled to about 120 C. and then made strongly alkaline to phenolphthalein by the addition of sodium hydroxide solution (aqueous 50 percent).
  • Diethanolamine 500 g. was added to serve as a distillation aid and pot-boiler after which the mixture was distilled with stirring at atmospheric pressure.
  • Piperazine 74.2 g. was distilled over in a yield of 28.7 percent.
  • the improvement which comprises the step of passing anhydrous hydrogen halide through the monoethanolamine hydrohalide pyrolysis mixture maintained at a temperature from about 215 to 250 C. at an hourly rate of flow from 0.58 to 4.40 moles of hydrogen halide per mole of rnonoethanolamine hydrohalide.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Catalysts (AREA)

Description

United States Patent Ofi ice 3,095,417 PROCESS F THE PREPARATION OF 1 PIPERAZINE Fdor Poppelsdorf, Charleston, and Richard C. Myerly, South Charleston, W. Va., assignors to Union Carbide Corporation, a corporation of NewYork NoDrawiug. Filed July 20, 1960, Ser. No. 44,005
Claims. (Cl. 260-268) However, the productivities obtained when the reaction was conducted in the absence of a catalyst, were unsatisfactory. In an attempt to increase the elficiency of the reaction, the :art resorted to the use of catalysts. The catalysts which are known in the art include zinc, iron, aluminum and magnesium halides, boric acid, ammonium chloride, and ammonium bromide.
However, none of the catalysts known to the art were satisfactory. In fact, actual experiments have shown that the yield obtained, when some of these catalysts were used, were far below the yields claimed. In other cases, the yields with these catalysts were no better than the yields obtained in non-catalytic pyrolysis.
' Thus, it is an object of th s invention to provide an economical and efiicien't process for the production of piperazine.
The process of this invention has at least two advantages over the prior arte-it makes possible the economical operation of a process below 250 C. and it provides increased productivities at a given reaction temperature.
The tact that the reaction proceeds at temperatures lower than '25 0 C. is important for at least two reasons. The, pyrolysis. of monoethanolamine hydrohalide is a very corrosive reaction. Thus, it is necessary to line the reactor to protect it from attack from the reaction products. The materials which are used as liners are tantalum, ceramic and glass. It is economically desirable to use glass as a liner'because ofits cost. However, glass-lined equipment does not stand up satisfactorily at temperatures above 250 C. The process of this invention allows glass to be used since it is conducted below 250 C.
Additionally, carbonization of the reaction product increases with temperature. The use of a lower temperature produces less carbonization which renders the product less viscous and easier flowing. This is an important feature in a continuous process.
It has now been discovered that the above objects can be obtained by carrying out the pyrolysis of monoethanolarnine hydrohalides in the presence of a catalyst selected from the class consisting of hydrogen chloride, hydrogen bromide, hydrogen iodide and hydrogen fluoride.
The monoethanolamine hydrohalides which can be employed as starting materials are rnonoethanolamine hydrochloride, hydrobromide, hydroiodide and hydrofluoride.
The efiect of the catalyst on the yields of piperazine can be shown from the following table in which the catalyst is hydrogen chloride and the hydrohalide is monoethanolamine hydrochloride.
3,095,417 Patented June 25, 1963 TABLE I Reaction Hydrogen Chlo- Yield 01 Reaction Time, ride Passed Piperazine, Temperature, 0. Minutes through Reaction Percent Mass 36.7 8.9 0.8 11.7 nll t} litll experiments were done at: atmospheric pressure with continuous s rrr b Hydrogen chloride gas passed into the reaction mass at the rate of 1.67 moles per hour per mole of monoethanolamine hydrochloride.
0 Dry nitrogen passed into the reaction mass at the rate of 1.5 moles per hour per mole of monoethanolamine hydrochloride.
The temperatures at which the reaction can be conducted are from about 215 C. to about 250 C. The preferred range is firom 220 C. to 230 C., at atmospheric pressure.
Monoethanolarnine hydrohalide is first prepared by treating monoethanolamine with an anhydrous hydrogen halide.
The particular proportions are not narrowly critical. The preferred concentration is a 1:1 molar ratio. The monoethanolamine hydrohalide formed is brought to the desired reaction temperature and anhydrous hydrogen halide, preferably hydrogen chloride, is passed through the molten mass with stirring. The amount of catalyst passed through-at atmospheric pressure can be from 0.1
to 4.0 moles per hour per mole of monoethanolamine A hydrohalide attenrperatures from 215 C. to 250 C The preferred range is 0.1 to 0.9 moles per hour.
The following table illustrates the effect of hydrogen chloride flow rate on the yield of piperazine.
TABLE II Dependence of the Catalytic Efiect on Hydrogen f Chloride Flow Rate 1 Hydrogen Chloride Flow Rate,- Moles Per Hour Yield of Per Mole Monoethanolamine H01 Piperazine,
' Percent;
1 Reaction temperature and time for each experiment were 220 to 225 C. and 330 minutes, respectively.
As will be noted from Table II there no advantage in increasing the flow rate beyond 0.80 mole per hour per mole of monoetha-nolamine hydrochloride when operating at this temperature range.
It is to be understood that at pressures higher than atmospheric lesser llow rates of catalyst will be operable since the hydrogen halides are then more soluble in the reaction mixture. It would appear that the flow rate at any pressure should be sufl'icient to maintain a molar ratio of monoethanolamine to anhydrous hydrogen halide of at least 1:1.
The pyrolysis can also be conducted in the presence of an inert dispersant. The nature of the dispersant is not critical. The only condition being that it is inert under the reaction conditions. Examples of dispersants include mineral oil, diphenyl ether, phenyl diphenyl ether, etc. The concentration of the dispersant is not critical and 3 can be from 30-l20 grams per mole of amine hydrohalide starting material.
The following table illustrates the catalytic efiect of anhydrous hydrogen chloride when the reaction is carried out in an inert dispersant.
TABLE III Evidence for the Catalytic Efiect of Hydrogen Chloride on the Pyrolysis in an Inert Dispersant of M onoethanolamme Hydrochlorzde to Pzperazine (a) Hydrogen Dispersant Chloride Passed Grains per Yield of Reaction Time, Hrs. through mole of Piperazine,
Reaction Monoeth- Percent Mass anolamine B All experiments were done at 245 to 250 C. at atmospheric pressure with continuous stirring.
b Mineral oil, B. Pt. 300 C.
Anhydrous hydrogen chloride passed into the reaction mixture at the rate of 1.67 moles per hour per mole of monocthanolamine hydrochloride The following examples illustrate the invention.
EXAMPLE I Anhydrous hydrogen chloride (219.0 g., 6 moles) was slowly passed with stirring into monoethanolamine (366.5 g., 6 moles). The resulting monoethanolamine hydrochloride was rapidly heated with stirring to 220-225 C., whereupon hydrogen chloride was passed continuously through the molten hydrochloride at the rate of 10.0 moles per hour, the gas being introduced by means of a sparging tube placed as far below the liquid surf-ace as possible.
The reaction mass was held with stirring under these conditions for /2 hours.
At the end of the reaction period, the product was cooled to about 120 C. and then made strongly alkaline to phenolphthalein by the addition of sodium hydroxide solution (aqueous 50 percent).
Diethylenetriamine (500 g.) was added to serve as a distillation aid and potboiler after which the mixture was distilled with stirring at atmospheric pressure. Piperazine (94.8 g.) distilled over in a yield of 36.7 percent.
EXAMPLE II The procedure of Example 1 was followed excepting that the hydrogen chloride treatment was omitted. Piperazine was obtained in a yield of 8.9 percent.
EXAMPLE III Monoethanolamine hydrochloride (6 moles) was rapidly heated with stirring to 220225 C. whereupon anhydrous hydrogen bromide was passed continuously through the molten hydrochloride at the rate of 2.35 moles per hour, the gas being introduced by means of a spar ging tube placed as far below the liquid surface as possible.
The reaction mass was held with stirring under these conditions for 5 hours.
At the end of the reaction period, the product was cooled to about 120 C. and then made strongly alkaline to phenolphthalein by the addition of sodium hydroxide solution (aqueous 50 percent).
Diethanolamine (500 g.) was added to serve as a distillation aid and pot-boiler after which the mixture was distilled with stirring at atmospheric pressure. Piperazine (74.2 g.) distilled over in a yield of 28.7 percent.
What is claimed is:
1. In the process for preparing piperazine by the pyrolysis of monoethanolamine hydrohalide to piperazine and recovering piperazine from the pyrolysis mixture, the improvement which comprises the step of passing anhydrous hydrogen halide through the monoethanolamine hydrohalide pyrolysis mixture maintained at a temperature from about 215 to 250 C. at an hourly rate of flow from 0.58 to 4.40 moles of hydrogen halide per mole of rnonoethanolamine hydrohalide.
2. The process of claim 1 wherein the monoethanolamine hydrohalide is monoethanolamine hydrochloride References Cited in the file of this patent UNITED STATES PATENTS 2,839,533 Scigliano et ai June 17, 1958 FOREIGN PATENTS 595,430 Great Britain Dec. 4, 1947 819,126 Great Britain Aug. 26, 1959

Claims (1)

1. IN THE PROCESS FOR PREPARING PIPERAZINE BY THE PYROLYSIS OF MONOETHANOLAMINE HYDROHALIDE TO PIPERAZINE AND RECOVERING PIPERAZINE FROM THE PYROLYSIS MIXTURE, THE IMPROVEMENT WHICH COMPRISES THE STEP OF PASSING ANHYDROUS HYDROGEN HALIDE THROUGH THE MONOETHANOLAMINE HYDROHALIDE PYROLYSIS MIXTURE MAINTAINED AT A TEMPERATURE FROM ABOUT 215* TO 250* C. AT AN HOURLY RATE OF FLOW FROM 0.58 TO 4.40 MOLES OF HYDROGEN HALIDE PER MOL OF MONOETHANOLAMINE HYDROHALIDE.
US44005A 1960-07-20 1960-07-20 Process for the preparation of piperazine Expired - Lifetime US3095417A (en)

Priority Applications (2)

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US44005A US3095417A (en) 1960-07-20 1960-07-20 Process for the preparation of piperazine
GB25911/61A GB979140A (en) 1960-07-20 1961-07-18 Improvements in and relating to the preparation of piperazine

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB595430A (en) * 1944-04-21 1947-12-04 Rhone Poulenc Sa Improvements in or relating to the preparation of piperazine
US2839533A (en) * 1956-03-12 1958-06-17 Dow Chemical Co Method for the preparation of piperazines
GB819126A (en) * 1958-03-20 1959-08-26 Arthur Abbey Method for the preparation of piperazines

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB595430A (en) * 1944-04-21 1947-12-04 Rhone Poulenc Sa Improvements in or relating to the preparation of piperazine
US2839533A (en) * 1956-03-12 1958-06-17 Dow Chemical Co Method for the preparation of piperazines
GB819126A (en) * 1958-03-20 1959-08-26 Arthur Abbey Method for the preparation of piperazines

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